Calorimeter.



S. W. PARE.

GALORIMETER.

APPLIouxoN FILED JUNE 24. 1912.

1 1 1 5,238. Patented 0015.27, 1914.

2 SHEETS- SHEET 1.

NIH"

HWINHM S. W. PARR.

GALORIMETER.

APPLICATION FILED JUNE 24, 1912. 1,1 15,238, Patented 0013.27, 1914.

2 SHEETS-SHEET Z. 45 2 ls \l fI 1 22 7 44a 27 s N 57 4f i 4f 2 i 2 l1Ji( i" dai-messes: Iwan/off 5eme/ Wfafr;

SAMUEL W. PARE, OF URBANA, ILLINOIS.

CALQBIMETER.

Specication of Letters Patent.

Patented Oct. 27, 1914.

Application led June 24, 1912. Serial No. 705,386.

To all whom it may concern.'

Be it known that I, SAMUEL W. Palm, a i

citizen of the United States, residing aty Urbana, county of Champaign,State of Illinois, have made new and useful Improvements inCalorimeters, of which the following is a specification.

Bomb calorimeters as ordinarily used are constructed of steel with theinner faces lined with platinum or with gold plated copper to resist thecorrosive action of the` nitric acid liberated in the calorimeter whenin use. Such constructions have the disadvantage of high cost, and alsothe disadvantage that moisture may work in under the lining andsubsequently impair the accuracy of the heat determination. Alsoplatinum linings as thus used within a calorimeter are easily damagedand are otherwise objectionable, asis Well known.

As the result of extended experiment and investigation I have discovereda new alloy` which is so resistant to the corrosive action of themoisture oxygen or of ordinary acids such as nitric acid that it can beused within the calorimeter and exposed directly to the action of thecalorimeter charge. The alloy is so resistant that it may be -used forvalve seats, and similar parts of the apparatus where the wear andexposure are extreme,

without appreciable corrosion or deteriora-` tion even after longcontinued use.

The drawings which accompany and form a part of the presentspecification show a calorimeter in which this new allow is usede forsubstantially' all of the exposed elements or parts.

This calorimeter is of novel construction in many parts and is welladapted for .use atV high `pressures in the determination of thecalorific values of coals, oils, and other coml bustibles.

In the drawing, Figure 1 is a perspective view illustrating the bomb orcalorimeter assembled ready for use. Fi 2 shows a bench plateserviceable as a soc et or wrench to hold thelcalorimeter cup while itscap is being screwed into place. Fig. 3 is a per.

spective view of the .upper parts of the calorimeter taken apart. Fig. 41s a perspec-y tive view of the cover.- Fig. 5 shows the calorimetercup. Fig. 6 is a perspective detail of one of the ad]ustable clamps usedto hold an endv of the ignition wire; and Fig. 7

l eters.

is a sectional elevation, somewhat enlarged, through the calorimetercover and its ass0- ciated parts.

The calorimeter cup l as shown in Fig. 5

is of cylindrical outline with a threaded enlargement 2 at its upper.portion and with an octagonal shoulder or ledge 3 to serve as a wrenchface or holding means when the cup has been dropped into the `benchplate 4 of Fig. 2. This bench plate is used to hold the cup when itscover is being adjusted into position for use or is bein removed afterthe combustion has taken p ace.

At the upper edge of the cup 1 is an annular rim which, as shown in Fig.7, has a Hat top face 5 and is beveled off at the outer corner 6 but isnot similarly beveled or rounded at the inner edge and consequentlypresents the square corner 7 which, as hereinafter explained, is ofmarked importance in insuring a tight connection between the cup and itscover.

The cover 8 of the calorimeter has an annular groove of rectangularcross-section in its lower face within which groove is seated an annulargasket or packing 9. This packing may be of organic material such asrubber4 or a rubber composition of the type heretofore commonly used forair tight packings but not regarded as feasible in bomb calorim- Gasket9 is of such dimensions that the cover sets down within the rim of thecup at 10. Preferably, the joint at 10 is a good mechanical t so thatthe rubber gasket 9 is in large measure shielded from direct contactwith the hot acid fumes developed in the calorimeter, but need not be aContact joint.

Fuel to be burned is held in a suitable cup 11 carried in the loopedlower end of a supnition wire 14 into position for use. Each of l Vtheseclamps is built up from a strip 15 bent in rectangular form and havingits ends overlap ed to yieldingly grip the supporting wire. (gne of theends is slotted at 16 so that when the fastening is squeezed between thefingers, it releases its grip on the supporting wire and can be movedupward or downward at will. This rectangular fastening 15 has one of itssides cut and punched to form a yielding tongue 17 behind which theignition wire 14 may be introduced and held. In practice the wire 14,cut to proper length and coiled up as desired, is slipped behind thetongue 17 and then both fastenings are pushed downward along thesupporting and guide wires 12 and 13 until the ignition wire 14 is atproper position with respect to the charge to be ignited in the crucible11.

The upper end of wire 13vpassesfthrough a tapered opening in the cover 8which opening is lined with an insulating bushing 18. An enlargement 19on wire 13 serves to tighten up the joint when wire 13 is drawn up bymeans of the threaded terminal 20. An insulating bushing or ring 21 anda smaller bushing 22 serve to keep the nuts 20 and 23 out of contactwith the metal of the cap while at the same time insuring perma* nencyto the joint.

A collar 24 overlaps the top of the cover and has screw-threadedengagement with the cup or lower member of the calorimeter so that whenthe collar is screwed down on the threads of the cup, it will serve todraw cap 8 and its packing 9 tightly against the upper rim of the cup,insuring a gas-tight connection throughout the entire circumference eventhough the pressures within the calorimeter may be many times that ofthe atmosphere. There is not room for the rubber to flow into the jointat 10.

Rising from the central portion of the cover 8 is a neck 25screw-threaded for engagement with a retaining collar 26 which grips theprotruding annular rim 27 of a nipple 28 and holds that nipple tightlyagainst the upstanding annular lip 29 which surmounts neck 25. Therubber gasket 30 similar to gasket 9 is interposed between the nippleand the lip of the neck and the nipple lits down within the neck with asnug mechanical joint at 31 directly comparable to the joint 10 betweenthe calorimeter top 8 and the main cup. Oxygen or other gas or gases maybe supplied throu h a tubular inlet 32 indicated somewhatdiagrammatically as supplied with an inlet pipeand valve 33 and anoutlet ipe and valve-34 and equipped with the suita le pressure deviceor gage 35.

The passage for gas into the calorimeter includes a cylindrical chamber35 within neck 25 which terminates in a constriction 36 below which isthe main valve seat 37 of the calorimeter inlet. The valve seat 37 is inthe form of an annular lip.

The inlet valve comprises a cylindrical valve stem 38 enveloped by aspiral closing spring 39 and carries at its upper end a solid block 40serving to retain the valve in operative engagement with the spring andhaving wrench sockets in its upper face to facilitate extreme lower endof the valve is flared out- -g wardly at 43 so that gases enterin thecalorimeter at high velocity will be de ected outward against the sideWall of the calorimeter body and so will not displace or disturb thecoal or other combustible within the crucible or cup 11 of theapparatus.

Under certain circumstances, it is desirable to admit gas to thecalorimeter under heavy pressure and then after combustion of the fuelto withdraw the products of combustion to another receptacle foranalysis or other treatment. As a means for accomplishing this the pushrod 44 is provided within the inlet tube 32, this push rod having ahandle 45 whereby it mav be screwed forward and into contact with block40 and thus unseat the valve and permit the high pressure gases toescape through valve 34 to an analyzing apparatus not shown.

Under some circumstances it is desirable to wash out the calorimeterwith gases or to otherwise exhaust or empty it of air or the like andfor convenience in carrying out these and similar manipulations, thecover 8 is equipped with an outlet tube 46 having a suitable cap or seal47 but so located that it can be unsealed when gases introduced Withinthe calorimeter are to be drawn oli' to auxiliary apparatus.

In the apparatus as thus described the main cup l, the cover 8, thecurrent supply wires 12 and 13, the valve and in fact all of the partsexposed to the corrosive action of the nitric acid and the likeintroduced or developed in the calorimeter are constructed of thespecial alloy which will now be described in detail.

In general this new alloy comprises nickel as its basis together with acertain amount of chromium and a somewhat smaller quantity of copper.The `chromium accentuates the resisting properties of the nickel buttends to increase the melting temperature and also leads to brittleness.The copper on the other hand tends to lower the melting point, though itcannot be used except in moderate quantity because of the danger ofcorrosion. I have found that there is also advantage in having tungstenpresent and while its presence may not be necessary yet it tends towardeasy casting and also strengthens the acid resisting properties of thealloy. Tungsten is much like chromium in promoting resistance to acidattack but it is quite in contrast with chromium in that it permits easycasting and reduces shrinkage. Aluminum, and manganese in vsnrallquantities can also be used to advantage, being added after the mass isfluid and when it is about in condition for pouring. The aluminum lowersthe melting point of the alloy, somewhat, and besides being a gooddeoxidizer, it accentuates the resistance to both nitric and sulfuricacid. Manganese serves much as aluminum. Titanium and boron infractional percentages may also be used.

I have found that the relative proportions of the elements above namedmay be varied through realtively Wide limits and still yield an alloyhaving, in the main, the mechanical strength and toughness and the acidresisting characteristics of metal suitable for use in calorimeters. Ihave found that the following composition gives good results: 68 percent. nickel, 8 per cent. copper, 18 per cent. chromium, 3 pe'r cent.tungsten, 2 per cent. aluminum, 1 per cent. manganese, .l2A

of 1 per cent. boron, and .05 of 1 per cent. titanium. A

As to variations from the above proportions, I have found that thecopper content may varybetween 5 per cent. and 11 per cent., thechromium content between 15 per cent. and 21 per cent., the aluminumbetween E of 1 per cent. and 3 per cent. and the manganese between of 1per cent. and 1% per cent. The manganese may be omitted altogether ifdesired, though I regard it as a substantial aid in casting and as adesirable deoxidizer. l 1

Boron from .02 of 1 per cent. to .2 of 1 per cent. may be resent withpossible advantages to the al oy. In practice I prefer to add to themelt .12 of 1 per cent. boron put v in as an alloy with manganese. Theboron besides acting as a deoxidizer appears to alloy with the nickelwith advantageous results. Some carbon and some iron may be present tothe extent of .1 of as may also slight quantities of silicon, and Whilethese are believed to do no good, they do not appear to be especiallyharmful.

The best melting and casting temperature for the alloy here disclosed 1nits various modifications is in the neighborhood of 1300 degreescentigrade, with 1500 degrees centigrade as the upper limit.

The alloy may be cast in iron molds not heated, or in sand, and whenthus made has a tensile Strength of about 55,000 to 60,000 pounds persquare inch. The cast material can be rolled and drawn into Wire and canbe spun and mechanically worked according to well known metallurgicalmethods. With drawn wire, the tensile strength is much greater than thatgiven for the cast material. The relatively great strength and toughnessof the alloy, even in cast condition, is of importance when the materialis cup 1 per cent,

square inch even under normal conditions.

The electrical resistance of the alloy is high, being in theneighborhood of fifty times that of copper.

The metal, either in cast or rolled condition is non-oxidizable in theordinary sense. Corrosion, if it occurs at all, at atmospherictemperature and pressure, when `100 square centimeters area is subjectedfor twentyour hours to four times normal HN()3 or H2304 or mixtures ofthese acids is so slight as to be substantially within the experimentalerror of weighing, even through the balance used may show changes of ,15of a milligram. As a result of continued useY of the device heredisclosed, it may be said that the total corrosion within the bomb evenunder extreme temperatures and pressures need not exceed of a milligramfor each heat and such a slight corrosion, assuming that it might takeplace, would introduce a variable of not more than one part in tenthousand, which, of course, is well Within the experimental accuracy ofmethods for using bomb calorimeters.

It is obvious that such an alloy is Well adapted for use in theconstruction of valves, of valve seats and the exposed portions ofchemical vessels, and in a continuing application Serial No. 821,593,filed February 27, 1914, claims have been made on the alloy, per se.

What I claim as new and desire to secure by Letters Patent of the UnitedStates is:

1. In a bomb calorimeter, a calorimeter of non-corrosive alloy threadedon lts exterior and having a projecting bearing run flat on top andformed with a square corner at its inner edge, an or anic gasket on Saidllat top, a cover close y overlap ing said square shoulder on the insideof t e cup to protect said gasket, and a collar threaded to said cup anddirectly engaging saidcover.

2. In a bomb calorimeter, the combination of a threaded cup having abearing rim flat on top and formed with a square corner at its inneredge, a cap having an extension depending within the cup beyond thebearing face of said rim, with a close fit between said rim and saidextension and an organic acking in tight engagement with the top ace ofsaid rim.

3. In a calorimeter, the combination of a cup, having a rim at its top,said rim having a fiat bearing face, and a cover having a gasket broaderthan said rim and contacting with the dat face thereof, said coverprojecting down and beyond said fiat face to shield said gasket fromdestructive agencies Within the calorimeter.

4. In a calorimeter, a cover, a pair of current supply wires suspendedfrom said cover, clips slidable over said wires, and an ignition wireremovably gripped by said clips.

. 5. In a calorimeter, a pair of parallel conductors, a cruciblesupported by one lof said conductors, a heating wire supported inproximity to said crucible and a yielding clip for each end of saidheating wire, said clips being movable alng said parallel wires to bringthe heating wire in advantageous position with respect to the charge inthe Crucible.

6. An adjustable clip for supporting the heating wire of a calorimeter,said clip consisting of a metal strip bent to the shape of a rectangleand having its overlapping ends relatively movable to yieldingly grip awire pasing therethrough and through the opposite side of the device,said fastenin having an integral tongue pressed from sai strip toyieldingly grip the end of the heating Wire thereby maintainingelectrical connection therewith.

7. In a calorimeter, a cup having a cover and means for sealing saidcover to said cup, said cover having a central opening and having a"valve positioned in said opening and arranged to deflect incoming gasesoutwardly against the sides of the calorimeter cup.

8. In a calorimeter, a cover having a centrally disposed neck with achamber therein, a spring within said chamber, a valve stem governed inits movement by said spring and a valve carried by said stem and seatingon an annular rim depending, from the under face of said cover. v

9. In a calorimeter, a removable cover having a gas passagetherethrough, a valve positioned centrally within. said cover to controlsaid passage and seating against an under face thereof, said valvecarrying a packing, said valve being shaped so as to shield said packingfrom thedestructive elements normally developed within the calorimeter.

10. In a calorimeter, a cover having a pas sage through its center, saidpassage havin an enlargement at its lower portion, a va ve fittingwithin said portion and carry ing a packing ring shielded from directContact with the corrosive agents within the calorimeter, said valvehavinga flaring portion to serve as a deiector for diverting outwardlyagainst the wall of the calorimeter, gases entering past the valve seat.

11. A calorimeter having a cup and a cover, the inner faces of which areexposed to direct contact with the acid normally developed in thecalorimeter, said faces being constructed of a non-corroding alloy,substantially as described.

12. A momb calorimeter having its Walls directly exposed to contact withthe corrosive agencies normally developed in the calorimeter, said wallsbeing constructed of an alloy containing approximately 68 per cent.nickel, 8 per cent. cop er, and 18 per cent. chromium, substantial y asdescribed.

13. A calorimeter cup unlined throughout and composed essentially of analloy of 68 pei' cent. nickel, 8 per cent. copper, 18 per cent. chromiumand 3 per cent. tungsten toether with a small percentage of deoxidizingmaterial. y

14. A calorimeter having a cup and a cover, the inner faces of which areexposed i to direct contact with the acid normally developed in thecalorimeter, said cover having a gas inlet therethrough. which isenlarged at the inner face of said cover to receiv\a\ val-ve, and avalve movable outward automatically under the expanding force of gaseswithin the calorimeter to seal said gas inlet.

In witness whereof, I hereunto subscribe my name to this specificationin the presence of two witnesses.

SAMUEL W. PARR. Witnesses:

I. V. GURRAN, PAUL W. BAUMANN.

cover, clips slidable over said wires, and an ignition wire vremovablygripped by said clips.

, 5. In a calorimeter, a pair of'parallel conductors, a cruciblesupported by one of saidy conductors, 'a heating wire supported inproximity to said crucible and a `yielding clip for each end of saidheating wlre, said clips being movable along said parallel wires anintegral tongue pressed from sai strip to yieldingly grip the end of theheating wire thereby maintaining electrical connection -therewith.

7. In a. calorimeter, a cup having a cover and means for sealing saidcover to said cup, said cover having a cent-ral opening vand havinga'valve positioned in said opening and -'arranged 4to deflect incominggases outctrretuons 1n Leners Patent 1110.1,1 15,238.

wardly against the -sides of the calorimeter cup. l

8.l In a calorimeter, a cover having a centrally disposed neck with achamber therein, a spring within said chamber, a valve stem governed inits movement by said spring and a valve carried by said stem and seatingon an annular rim dependingl from the under face of said cover.

9. In a calorimeter, a removable cover having a gas 'passagetherethrough, a valve positioned centrally within said cover .to controlsaid passage and seating against an under face thereof, said valve`carrying a packing, said valve being shaped so as to shield saidpacking from the'destructive ele- -ments normally developed within thecal- 410. In a, calorimeter, a cover having a passage A through itscenter, said passage hav-- 1 n an enlargement at its lower portion, a vave fitting within said portion and carrying a packing ring shielded fromdirect contact with the corrosive agents within the calorimeter, saidvalve having'a Haring portion to serve as a detlector for divertingoutorimeter, said walls being constructed of'- an alloy containingapproximately 68 per cent. nickel, 8 per cent. copper, and 18 per cent.chromium, substantially as described.

13. A calorimeter cup unlined throughout and composed essentially of analloy of 68 per cent. nickel, 8 per cent. copper, 18 per cent. chromiumand 3 per cent. tungsten to- -gether with a small percentage ofdeoxidizf ing material. 14. A calorimeter having a cup and a cover, theinner faces of which are exposed veloped in the calorimeter, said coverhaving a gas inlet therethrough which is enlarged at the inner face ofsaid cover to receix'aval've, and a valve movable outward automaticallyunder the expanding force of gases within the calorimeter to seal saidgas inlet. In witness whereof, I hereunto subscribe my name to thisspecification in the presence 'of two witnesses.

It is hereby artista that inr Letters Patent No. 1,115,238, mattaOctober 27, 1914, upon the tpplication of Samuel-VV. Parr, of Urbana,Illinois, for an improvement in Calorimeters, errors appear in theprinted specificationrequiring co1'- rectionas follows: Page 1, line 24,for the word moisture read moist; page 3, line 15,l forthe worrealtively read relatively; page `et, line 63, for the word,mo 1nb Iread bomb; and that the saidv Letters Patent should be read withthese-corrections therein that the same may conform to the record of thecase in the Patent Olice'.

Signed and sealedl this 1 7 th day of November, A. D., 1914.

a.` F.. WHHEHEAD,

Act/ng ofPatents.

I' to direct contact with the acid normally d`e Gorrectlonsvin LettersPatent No. 1,115,238.

11 is hreby @rained that in nemers ramt No. 1,115,23s,gm1ed ocwbr 27,1914, upon the `vgpplieation of Samuel W. Parr, of Urbana, Illinois, foran improvement in Calorimeters, elrrors appear in the printedspeciton'requiriug correction as follows: Page Lvlrne 24, for the word1moisture read moist; page 3, line 15, for the word realtirely readrelatively; page 4, line 63, for the word momb read bomb; and that thesaid Lettere Patent should be read with these-corrections therein thatthe same may conform to the record of the case in the Patent Oioe.

Signed and seeled this 17th clay of November, A. D., 1914. [mn] rc.` F..WHLTE'HEAD,

Act/ng Commsofwr of Patents.

